Manufacture of imidazolines



2,215,864 V MANUFACTURE OF mnnazonmns Edmund Waldmann, Klosterneuburg, and August v Chwala, Vienna, Germany, assignors, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware i No Drawing. Application Marchzz, 1939, Serial No. 263,396. InAustria April 4, 1936 whims. (c1; 260 -309) This. application is afcontinuation-in-part of:

application Serial No, 94,120, filed August 3, 1936. This invention relates to the manufacture of imidazolines containing aliphatic radicals ofhigh acid and such a diamine mono-acylated with a fatty acid of high molecular weight, in which the two amino groups are bound to two carbon atoms adjacent to each other, one of which amino molecular,weight'as'substituents atthe 2-carbon groups contains two hydrogen atoms and the atom byheating with a fattyacidor a carboxylic other at least one hydrogen atom. acid or high molecular weight to high tempera In the preferred mode of operating, the mixglazes, greggrably to temperatures lying between ture made in accordance with the invention is an C., a mixture consisting on the one heated to a'temperature of '250-290 C. If, for handflof a ,base having a primary amino-group example, there is used a quantity of lauric acid, and a second primary or secondaryamino-group, ethylenediamine and ethylenediaminehydrochlm which are in 1:2-position to eachother, the two ride the hydrochloride which forms a sediment carbon atoms in 1:2-position being linked by a dissolves veryaquickly in this interval of temperasingle bond, and on the other hand a salt of such. 1 ture, even with only gentle stirring, and at the .15 base formed from a strong acid. same timecauses formation of the undecyl-imid- Suitable bases having aprimary amino-group azolinehydrochlorlde. This reaction may also be and a second primary or secondary amino-group conducted at a temperature lower than 250 C. in 1:2-position to each other are 'ethylenediaby heating for a longer period. The use of a vac- 1133;? prfggiuctsi H0? ctlietliylenetgian'iinne, Zrifun:l during the second half of the condensation e ene ram ne, e rae y enepen am e; os a van geous. mologues of ethylenediamine such as 1:2-propyl- When the condensation to the imidazoline deeiliediaminie, 2z3 -butylenediamine, N-methylethrivative starts from a mixture of fatty acid amine yenediam ne. and aminehydrochloride, the three components Suitable strong acids for forming the salts are of the mixture are advantageously selected so in particularmineral acids, such as hydrochloric that for 1 mol of the fatty acid or its derivative 5 jaiiid, hydrobromic'acid, sulfuric acid, and the there are at least 1 mol of the diamine and the e. v salt-like bound mineral acid. In using 1 mol of Suitable fatty acids of high molecular weight lauric acid therefore, there should be /2 mol ethare in general aliphatic acids containing more ylenediamine and /2 mol ethylenediaminehydrothan 8 carbon atoms,for instance caprylic acid, chloride, corresponding with the equation lauric acid, stearic acid. palmitic acid, oleic acid, ,H H,+2 C1 also mixtures of these acidsobtainable by sapone r ifyingnatural fats like olive oil, tallow, palm oil; T

it also cycloaliphatic acids .such as naphthenic n u :0 acids alld the like. 1 N... QH,

Instead "of the fatty acids there may be used suitable derivatives thereof such as esters, g ERg h g m h hydmchmde of nude amides, anhydrides or halides; according to the w the, lauflc acid derivative, there is selection of the derivative to be used, the simul-, h dilauro 16th lenediamme which for taneous use of the free base or the salt ofthe c osenl algead contai or 40 base may, ifde'sired, be omitted, for in the case in? g. i b und te ga g i of halides the suitable mixtures leading to. the 8 a i a m desired result are formed, due to the mineral this 1s Peatedwlth 1 mol Ethyleneacid becomingfree, in the course of .theacylation. ,diammfehyd-rochlonde about 250*290 there Quite generally,v the new process consists in 15 obtained the reaction in the sense of the fol- 45 heating with a product selected, from the group 9W equation consisting of fatty acids of high molecular weight quH ooNncefllNnooouHa+NH,o=H,NH,.2H0l and thesalts, amides, halides and esters thereof, a mixture consisting on the one hand of a base a ,50 which issubstituted at two carbonatomsadjaso cent to each other by an amino-group each, of V N H,

which amino-groups one contains two hydrogen C atoms and the other at least'one hydrogenatom, th p d ns a a n und y udaz linehyand on the other hand of a salt of such basewith drochloride in approximately quantitative y da strong acid, the heating being carried out at a l If, h the parent material is the mono- 55 h m -a v i laur'oylethylenediaminehydrocilloridef \ivavchichi al; The procedure may also be such that first of eady contains in itself per mol 37 M d all the salt of the mono-acyl compound is premol of ethylenediamine and 1 mole of hydropared. The process then consists in heating to chloric acid, it sumces to heat this hydrochloride in a high temperature a salt fonned from awstrong by itself to about 250-300 C. in order to obtain an excellent yield of the hydrochloride of undecylimidazoline. This reaction can also be carried out with the other mono-acyl-derivatives which are obtained from the diamines and the fatty acids of high molecular weight mentioned. in paragraphs 2 and 4 of this specification.

Under the effect of the amine salt, particularly the hydrochloride, high temperature of reaction evidently an elimination of the acid amide at first formed (as may be seen particularly clearly from the example of dilauroylethylenediamine) and then a combination of the eliminated material directly to the imidazoline hydrochloride. Philipps (Journal of the Chemical Society of London, 1928, page 2393 and following; Chemisches Zentralblatt 1928, vol. 2, page 2466) is of the opinion that the formation of benzimidazoles or imidazolines from the acyl-derivatives of the corresponding diamines by boiling with hydrochloric acid occurs of itself in such a manner that the acid amide is first saponified and the eliminated portion united directly to the benzimidazol or imidazoline.

These imidazolines of high molecular weight in the. form of their salts are freely soluble in water; solutions foam and have good capillary active properties. They may be used with advantage for improving dyeings on vegetable fibers.

Sulfo-groups may be introduced in their molecules by the methods which have become known from French Specification No. 796,917. These imidazoline-sulfonates of high molecular weight are also valuable as wetting, foaming, washing, emulsifying and dispersing agents. They are valuable as assistants in the textile industry.

The following examples illustrate the invention, the parts being by weight:

- Example 1 Into a stirring vessel provided with a thermometer and an inverted condenser there are charged 284 parts of stearic acid, 93 parts of ethylenediaminehydrochloride, 56 parts of ethylenediaminehydrate. The mixture is heated while stirring to C. and the temperature is raised within 90 minutes to 185 C., whereby between 1'70 and 185 C. a small proportion of a clear liquid distils (ethylenediaminehydrate and water). The

mixture is now heated within 30 minutes to 230 C. and then within 15 minutes to 290 C. The mass is kept for a short time at this temperature. which may be raised to 300 C. until a sample of the mass, tested with water, shows that it is soluble in water to a clear solution; the heating is then interrupted and the mass cooled. The brownish mass, which is crystalline when cold, consists almost exclusively of heptadecylimidazm linehydrochloride.

A free base may be separated in known manner by dissolving the hydrochloride with water and liberating the base with an alkali-hydroxide which can then be directly filtered or extracted by means of benzene. the product may be crystallized from a. mixture of 3 parts of methyl alcohol and 1 part of water, whereby 2-heptadecylimidazoline is obtained in crystalline scales melting at 94-95 C.

. Example 2 In an apparatus such as is described in Example 1 there is heated a mixture of parts of lauric one finds at comparatively For further purification is clearly soluble in wa- Example 3 In an apparatus such as is describedin Example 1 there is heated to 180 C. a mixture of parts of oleic acid, 15 parts of ethylenediaminehydrate; the mass which at first is somewhat foamy boils finally-gently as soon as the water has been distilled. After cooling to 120 C. there are added another 15 parts of ethylenediaminehydrate and heating is renewed to C. 37.5 parts of ethylenediaminehydrochloride are now added, whereupon the temperature of the mass is raised to 280 C. within 15 minutes and kept there for 10 Example 4 10 parts of oleic acid ethylester, 2 parts of ethylenediaminehydrate, 3 parts of ethylenediaminehydrochloride are heated together in the manner described in Example 1, save that the temperature of the mass for the saponification of the ester is allowed to remain for some time (about 5-10 minutes) at 120-l30 C. The aqueous solution of the heptadecenylimidazolinehydrochloride is treated with some active carbon and the free base is liberated by means of caustic soda; it is obtained in very good yield.

Example 5 I 8.5 parts of N-N-di-lauroylethylenediamide are heated with 3.3 parts of ethylenediaminehydrochloride in an open flask, while stirring, in such a manner that'after 5-10 minutes the mixture has a temperature of about 270-280 C. The, heating is continued for another 10 minutes to 280-290 C., whereby the greater quantity of the hydrochloride passes into solution. A sample then dissolves clearly in water.

Caustic soda solution precipitates from the aqueous solution the u'ndecylimidazoline which is the product of reaction in approximately quantitative yield.

Example 6 10 parts of mono-lauroylethylenediaminehydrochloride are heated for 5-10 minutes to 260- 280 C. and then for a further 5-10 minutes to 285-295? C. The hydrochloride of the undecylimidazoline is thus formed. A similar result is obtained by substituting the corresponding hydrobromide or sulfate for the mono-lauroylethylene-diamine-hydrochloride or by using instead of the mono-lauroylethylene-diamine-hydrochloride a derivative acylated with another fatty acid of high molecular weight, such as for example the mono-stearoyl-, the mono-oleoyb, the monopalmitoyl-, the mono-capryloyl-ethylenediamlne% hydrochloride, or finally by using the correspond ing 1.2-propylenediamine or 2.3-butylene-diamine derivatives.

Example 7 parts of oleic acid hydrochloride are introduced drop by drop, while stirring and cooling, into 48 parts of ethylenediaminehydrate. The mixture is then heated within half an hour to 280 C. to 300 C. and kept at this temperature for 10 minutes. The hepta-decenylimidazolinehydrochloride Obtained is a brownish melt which readily dissolves in water.

Example 8 18 grams of nonylic acid chloride are mixed, while well cooling,lwith 11 grams of diethylenetriamine and the mixture is gradually heated to 280 C. until the melt dissolves clearly in water.

The Z-octyl-l-aminoethyl A2 imidazolinehydrochloride thus obtained forms a brown paste; it readily dissolves in water with formation of foam and from its solution it may be transformed into the base by means of alkalies.

We claim:

1. Process for the manufacture of 2-substituted imidazolines which comprises reacting one mol of a product selected from the group consisting of the fatty acid halides and naphthenic acid halides with one mol of a base which is substituted at two carbon atoms adjacent to each other and linked by a single bond by an amino group each, 01! which amino groups one contains two hydro gen atoms and the other at least one hydrogen atom, the reaction being carried out at a high temperature.

2. Process for the manufacture of 2-substituted imidazolines which comprises reacting one mol of a product selected from the group consisting of the fatty acid halides and naphthenic acid halides with one mol of a base which is substttuted at two carbon atoms adjacent to each other and linked by a single bond by an amino group each; of which amino groups one contains two hydrogen atoms and the other at least one hydrogen atom, the reaction being carried out at a high temperature while using an excess of the free base.

3. Process for the manufacture of 2-substituted imidazolines which comprises reacting one mol of a product selected from the group consisting of the fatty acid halides and naphthenic acid ha1- ides with one mol of a base which is substituted at two carbon atoms adjacent to each other and linked by a single bond by an amino group each, of which amino groups one contains two hydrogen atoms and the other at least one hydrogen atom, the reaction being carried out at temperatures lying between 200 C. and 300 C.

4. Process for the manufacture of 2-substituted imidazolines which comprises reacting one mol of a product selected from the group consisting of the halides of the fatty acids containing 10 to 18 carbon atoms with one mol of ethylene diamine, the reaction being-carried out at temperatures lying between 200 C. and 300 C.

EDMUND WALDMANN. AUGUST CHW ALA. 

